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芳烃与原位生成的重氮烯烃参与1,3-偶极环加成
作者:小柯机器人 发布时间:2023/5/28 15:24:52

美国南加州大学Fokin, Valery V.团队报道了芳烃与原位生成的重氮烯烃参与1,3-偶极环加成。相关研究成果发表在2023年5月22日出版的《自然—化学》。

经典的1,3-偶极环加成已被广泛用于有机合成中,用于构建各种杂环。然而,在其长达一个世纪的历史中,简单而普遍存在的芳香苯环仍然是一个顽固的不活泼的亲偶极分子。

该文中,研究人员报道了由乙酰锂和N-磺酰基叠氮化物原位生成的芳香基团和重氮烯烃之间的1,3-偶极环加成。该反应产生密集官能化的环状磺酰胺吲唑,其可以进一步转化为在有机合成中重要的稳定有机分子。芳香基团参与1,3-偶极环加成拓宽了重氮烯烃的合成用途,重氮烯烃是一个迄今为止很少被探索的偶极家族,在其他方面很难获得。该方法提供了一种合成药用相关杂环的途径,并且可以扩展到其他含芳烃的起始材料。对所提出的反应途径的计算检查揭示了一系列精心策划的键断裂和键形成事件,这些事件最终生成环化产物。

附:英文原文

Title: Arenes participate in 1,3-dipolar cycloaddition with in situ-generated diazoalkenes

Author: Aggarwal, Shubhangi, Vu, Alexander, Eremin, Dmitry B., Persaud, Rudra, Fokin, Valery V.

Issue&Volume: 2023-05-22

Abstract: The venerable 1,3-dipolar cycloaddition has been widely used in organic synthesis for the construction of various heterocycles. However, in its century-long history, the simple and omnipresent aromatic phenyl ring has remained a stubbornly unreactive dipolarophile. Here we report 1,3-dipolar cycloaddition between aromatic groups and diazoalkenes, generated in situ from lithium acetylides and N-sulfonyl azides. The reaction results in densely functionalized annulated cyclic sulfonamide-indazoles that can be further converted into stable organic molecules that are important in organic synthesis. The involvement of aromatic groups in the 1,3-dipolar cycloadditions broadens the synthetic utility of diazoalkenes, a family of dipoles that have been little explored so far and are otherwise difficult to access. The process described here provides a route for the synthesis of medicinally relevant heterocycles and can be extended to other arene-containing starting materials. Computational examination of the proposed reaction pathway revealed a series of finely orchestrated bond-breaking and bond-forming events that ultimately lead to the annulated products.

DOI: 10.1038/s41557-023-01188-z

Source: https://www.nature.com/articles/s41557-023-01188-z

期刊信息

Nature Chemistry:《自然—化学》,创刊于2009年。隶属于施普林格·自然出版集团,最新IF:24.274
官方网址:https://www.nature.com/nchem/
投稿链接:https://mts-nchem.nature.com/cgi-bin/main.plex